Manufacturing method for solid processing composition for processing silver halide light-sensitive photographic material

ABSTRACT

A manufacturing method for a solid processing composition for processing a silver halide photographic light sensitive material, wherein the composition is manufactured by using a stirring granulation method, and at least part of said stirring granulation is performed in the temperature range of 35° C. to 120° C. 
     The manufacturing method for the solid processing composition mentioned above, wherein the content of the added solution in the stirring granulation process is 0.01 to 2.0 weight % of the total weight of said solid processing composition and wherein not less than 60% of the total weight of said solid processing composition has particle size of 1.0 μm to 150 μm. 
     The solid processing composition mentioned above may contain reductone derivative, sugar derivative and polyethylene glycol derivative.

FIELD OF THE INVENTION

The present invention relates to a manufacturing method for a solidprocessing composition for processing a silver halide light sensitivephotographic material, particularly to providing a manufacturing methodfor a solid developing composition.

BACKGROUND OF THE INVENTION

Photographic silver halide materials are generally exposed imagewisely,developed, fixed, washed with water, and then dried, thereby thephotographic image is finally observed.

The processing composition used in these process are provided asconcentrated solution kits, thereafter these kits are diluted whenpractically used as working solutions. The concentrated solution kitshave an advantage from the viewpoint of excellent solubility, moreover,since there can be wide range of selection of agents including liquidstate raw materials, thereby the concentrated solution kits are preparedat less burden in manufacturing processes and at low manufacturing cost.

However, the concentrated solution kits have some dangerous problem suchas a contact with skin. Especially the problem becomes more serious whenthese kits penetrate into eyes. Moreover, the kits must need heavyplastic bottles to contain them. Excessive weight and large volume ofprocessing vessels not only causes increasing transportation cost butalso environmentally unacceptable problem with large amount of disposalof the waste vessels.

Accordingly, from the viewpoint of small light weight and compact, theprocessing composition in the kits is preferably a solid such as apowder form, a granule form, and a tablet form.

However, as mentioned above, compared with a liquid form, a solid formhas a big problem in manufacturing cost because it must be passedthrough various processes, namely, process of measuring raw materials,mixing process, pulverizing process, granulating process, dryingprocess, and dressing process, furthermore, in the case of a tabletform, compressed tableting process is included.

Accordingly, to supply the solid form to the market at similar price tothat of the liquid form, there exists the subject that attains to lowerthe manufacturing cost of the solid form. On the other hand, there is aproblem of the deterioration of the properties of the solid processingcomposition, such as the occurrence of dust, the lowering of it'sstability, and the lowering of it's solubility.

SUMMARY OF THE INVENTION

An object of the invention is to provide a manufacturing method for asolid processing composition with a large cut down of manufacturingcost, further, to provide a manufacturing method for a solid developingcomposition with a preferable handling property, namely, a soliddeveloping composition with improved solubility, with stability in themanufacturing step, and with stability with the passage of time.

DETAILED DESCRIPTION OF THE INVENTION

Above object of the present invention can be accomplished by thefollowing constitutions:

1. A method for manufacturing a solid processing composition forprocessing a silver halide light sensitive photographic material,wherein the composition is manufactured by a stirring granulation methodcomprising a stirring granulation process, and at least part of saidstirring granulation process is performed under the temperaturecondition of 35° C. to 120° C.

2. The method for manufacturing the solid processing composition of item1, wherein the content of the added solution in the stirring granulationprocess is 0.01 to 2.0 weight % of the total weight of said solidprocessing composition.

3. The method for manufacturing the solid processing composition of item1, wherein not less than 60% of the total weight of said solidprocessing composition has particle diameter of 1.0 μm to 150 μm.

4. The method for manufacturing the solid processing composition of item1, wherein the composition contains reductone derivative represented bythe following formula (1): ##STR1## wherein R₁ and R₂ independentlyrepresent a hydroxy group, an amino group, an acylamino group, analkylsulfonylamino group, an arylsulfonylamino group, analkoxycarbonylamino group, a mercapto group or an alkylthio group; and Xrepresents an atomic group necessary to form a 5- or 6-membered ring.

5. The method for manufacturing the solid processing composition of item1, wherein the composition contains at least one kind of sugar and thecompound represented by the following formula (2):

    HO--(A.sub.1 --O)m.sub.1 --(A.sub.2 --O)m.sub.2 --(A.sub.3 --O)m.sub.3 --Hformula (2)

wherein A₁, A₂ and A₃ independently represent a substituted or anunsubstituted straight or branched alkyl group and these may be the sameor different, m₁, m₂ and m₃ independently represent an integer of 0 to500, provided with m₁ +M₂ +m₃ ≧5.

6. The method for manufacturing the solid processing compositiondescribed in item 3, wherein the solid processing composition is moldedas a tablet form by compression molding method.

Next, the invention will be explained in detail.

The solid processing composition of the invention is manufactured byusing a stirring granulation process. The following is the explanationfor the granulation in the invention.

The granulation is identified with manufacturing the grains which haveapproximately unified shape and size made from powdery, massive, andliquid raw materials. As for the granulating processes, it is possibleto use any of the well known processes such as the process of a rollinggranulation, an extrusion granulation, a compression granulation, apulverizing granulation, a stirring granulation, a fluidized bedgranulation and a spray-drying granulation, wherein the method formanufacturing the solid processing composition of the invention is thestirring granulation method.

The stirring granulation method is the method to utilize theagglomeration property of powder and this method is excellent in mixingability. According to this method, the granulation is performed bystirring powder as a raw material and a small amount of solution withstirring blade in a fixed vessel.

At least part of the stirring granulation process is performed under theatmosphere of 35° C. to 120° C., preferably 50° C. to 90° C.Furthermore, it is preferable that the atmosphere is kept duringstirring.

The stirring granulation process comprises at least 3 steps which are,(1) mixing ingredients for composition, (2) granulating by pouringsolution, and (3) stirring the mixture after pouring. The time requiredto perform part of the stirring granulation process is 0.5 minute to 180minutes, preferably 3.0 minutes to 90 minutes, especially preferably 10minutes to 60 minutes.

As for the method to maintain the atmosphere of not less than 35° C., itis preferable to adjust the stirring heat generated in high speedstirring. Furthermore, it is preferable to circulate the warm water orwarm oil through the jacket fixed beforehand around the mixing vessel ofstirring granulation machine, and it is also preferable to adjust thetemperature by changing air pressure in the vessel shut tightly. It ispreferable that the temperature in the vessel is measured periodicallyby equipping the thermometer such as a thermoelectric thermometer.

As for the solution added in the stirring granulation process, thesolution means not only water and organic solvents but also the solutionmade from binder dissolved in water or organic solvents.

In this invention, the amount of the solution added in the stirringgranulation process is 0.01 to 2.0 weight % of the total weight of thesolid processing composition of the invention, preferably 0.05 to 1.5weight %, more preferably 0.1 to 1.0 weight %.

In the manufacturing process of the solid processing composition of theinvention, mixing, pulverizing, and granulating of raw materials usedfor photographic processing agents is performed in only one process, andthis process is performed in granulation mixing vessel. Other processessuch as drying process and dressing process are omitted. According tothis method, the manufacturing cost can be largely reduced.

Accordingly, one to a few specified raw materials used for photographicprocessing agents are added into the mixing vessel and stirred formixing, thereafter, by keeping stirring, the granulation is performedadding the solution.

The solution can be poured during stopping stirring in the mixingvessel. However, from the viewpoint of unified dispersion of thesolution, it is preferable to pour the solution during stirring.

Depending on the kind of raw materials used for photographic processingagents, the time required to stir for mixing is preferably 3 seconds to120 minutes, more preferably 10 seconds to 60 minutes, especiallypreferably 30 seconds to 30 minutes.

The time required to pour the solution is 1 second to 30 minutes,preferably 10 seconds to 15 minutes, more preferably 30 seconds to 5minutes. It is preferable to keep stirring to facilitate granulationafter pouring the solution represented by water.

Stirring time after pouring the solution is 30 seconds to 90 minutes,preferably 1 minute to 60 minutes, more preferably 5 minutes to 30minutes.

Preferably not less than 60% of the total weight of the solid processingcomposition of the invention is occupied after granulation process withsolid grains whose particle diameter is 0.1 μm to 150 μm, morepreferably, not less than 70%, furthermore preferably, not less than 80%of the total weight of the solid processing composition of the inventionis occupied with solid grains whose particle diameter is 0.1 μm to 150μm.

As for the method of measuring the particle diameter of the solidgrains, it is possible to use any of the well-known method such as themethod of a sieve analysis, a microscopic analysis, a call-counteranalysis, a sedimentation analysis, a centrifuge analysis, a wind-sieveanalysis, a diffusion analysis, an adsorption analysis and atransmission analysis. The particle diameter is measured with the sieveanalysis in this invention and means an average particle diameterobtained by calculating particle distribution measured with this sieveanalysis.

The bulk density of the solid processing composition of the invention ispreferably 0.05 g to 2.0 g/cm³, more preferably 0.1 g to 1.5 g/cm³.

As for the structure of stirring granulation machine, it has preferablya rotating axis protruded from the bottom of the mixer and stirringblade is equipped around the axis. The preferable number of the stirringblade is one to ten, more preferable two to five. As for the usefulstirring blades, they are usually available on the market and can beeasily obtained.

The rotation rate of the stirring blades is 50 to 5000 rpm, preferably100 to 3000 rpm, more preferably 300 to 2000 rpm.

Hereinafter, reductone derivative included in the solid processingcomposition of the invention is explained in detail.

In formula (1), R₁ and R₂ independently represent a hydroxy group, anamino group (for example, an ethyl group, a n-butyl group, ahydroxyethyl group, and the other alkyl group having 1 to 10 carbonatoms as a substituent on this amino group), an acylamino group (forexample, an acetylamino group, a benzoylamino group), analkylsulfonylamino group (for example, a methanesulfonylamino group), anarylsulfonylamino group (for example, a benzenesulfonylamino group, ap-toluenesulfonylamino group), an alkoxycarbonylamino group (forexample, a methoxycarbonylamino group), a mercapto group or an alkylthiogroup (for example, a metylthio group, an etylthio group). R¹ and R² arepreferably a hydroxy group, an amino group, an alkylsulfonylamino group,an arylsulfonylamino group. X represents an atomic group necessary toform a 5- or 6-membered ring, preferably consists of a carbon atom, anoxygen atom or a nitrogen atom. X and vinyl group on which R₁ and R₂substitute and carbonyl group can together form a 5- or 6-membered ring.For example, X represents --O--, --C(R₃)(R₄)--, --C(R₅)═, --C(═O)--,--N(R₆)--, --N═ and two or three groups of these representative groupsare needed to form a 5- or 6-membered ring together with vinyl group onwhich R¹ and R² substitute and carbonyl group.

Wherein R₃, R₄, R₅ and R₆ independently represent a hydrogen atom, analkyl group having 1 to 10 carbon atoms which can be substituted (forexample, a hydroxy group, a carboxy group, a sulfo group as asubstituent), a hydroxy group and a carboxy group. Further, this 5- or6-membered ring may form a saturated and an unsaturated fused ring.

The example of the 5- or 6-membered ring includes a dihydrofuranonering, a dihydropyrone ring, a piranone ring, a cyclopentenone ring, acyclohexenone ring, a pyrrolinone ring, a pyrazolinone ring, a pyridonering, an azacyclohexenone ring and an uracil ring, and the preferableare a dihydrofuranone ring, a cyclopentenone ring, a cyclohexenone ring,a pyrazolinone ring, an azacyclohexenone ring or an uracil ring.

Further, the compound represented by formula (1) can form salts withlithium, sodium, potassium and ammonium.

The example of the compound represented by formula (1) in the inventionis listed below, but is not limited thereto. ##STR2##

The especially preferable compounds in the exemplified compoundsdescribed above are ascorbic acid and erythorbic acid (steric isomers).

The solid developing composition of the invention contains the compoundrepresented by formula (1) in an amount of preferably 20 to 99 weight %,and more preferably 30 to 90 weight %.

An amount of these reductone derivatives added into the processingsolution for exposed material is 0.1 to 100 g per liter for practicaluse, and 0.5 to 70 g per liter is preferable to prevent the formation ofwhite precipitation.

As for the preferable particle diameter of the reductone derivativesrepresented by formula (1) as a raw material before stirring, not lessthan 60% of the total weight of the reductone derivative has theparticle diameter of 150 μm to 1000 μm, more preferably not less than70% of the total weight of the reductone derivatives has the particlediameter of 150 μm to 600 μm, especially preferably, not less than 80%of the total weight of the reductone derivatives has the particlediameter of 150 μm to 300 μm.

The solid processing composition of the invention preferably contains atleast one kind of sugar derivative and/or the compound represented byformula (2) in an amount of preferably 0.5 to 30 weight % of the totalweight of the solid processing composition, and especially preferably 3to 20 weight %.

The sugar in this invention includes not only a monosaccharide and apolysaccharide which is obtained by forming glycosido-bonding of pluralmonosaccharides but also their decomposition compounds.

The monosaccharide is the generic name of the wide range of derivatives,including a polyhydroxyaldehyde, a polyhydroxyketone, their reductionderivatives, their oxidation derivatives, their deoxy derivatives, theiramino derivatives and their thio derivatives. Most of sugars arerepresented by generic formula C_(n) H_(2n) O_(n), and in thisinvention, monosaccharide is defined as not only the generic formulaC_(n) H_(2n) O_(n) but also the compound derived from this genericformula C_(n) H_(2n) O_(n). Among them, preferable is a sugar alcoholhaving primary and secondary alcohol which is obtained by reducingaldehyde group and ketone group.

Polysaccharide includes a cellulose derivative, a starch derivative anda glycogen derivative. The cellulose derivative includes a celluloseether derivative, wherein part or all of hydroxy groups of cellulosederivative are etherealized. The starch derivatives include dextrinderivatives which are various decompositions produced in the process offinally obtaining malt sugar through hydrolysis of the starchderivatives. It is preferable that the cellulose derivatives exist inthe form of salts together with alkali metals from the viewpoint ofsolubility. Among these polysaccharide derivatives, a cellulosederivative, a dextrin derivative and a cyclodextrin derivative arepreferably used, more preferably used is the cyclodextrin derivative.

The example of the monosaccharide derivative of the invention is listedbelow, but is not limited thereto.

Exemplified Compounds

B-(1) Glycerualdehyde

B-(2) Dihydroxyacetone

B-(3) D-Erythrose

B-(4) L-Erythrose

B-(5) D-Threose

B-(6) L-Threose

B-(7) D-Ribose

B-(8) L-Ribose

B-(9) D-Arabinose

B-(10) L-Arabinose

B-(11) D-Xylose

B-(12) L-Xylose

B-(13) D-Lyxose

B-(14) L-Lyxose

B-(15) D-Xylulose

B-(16) L-Xylulose

B-(17) D-Ribulose

B-(18) L-Ribulose

B-(19) 2-Deoxy-D-ribose

B-(20) D-Allose

B-(21) L-Allose

B-(22) D-Altrose

B-(23) L-Altrose

B-(24) D-Glucose

B-(25) L-Glucose

B-(26) D-Mannose

B-(27) L-Mannose

B-(28) D-Gurose

B-(29) L-Gurose

B-(30) D-Idose

B-(31) L-Idose

B-(32) D-Galactose

B-(33) L-Galactose

B-(34) D-Talose

B-(35) L-Talose

B-(36) D-Quinovose

B-(37) Digitalose

B-(38) Digitoxose

B-(39) Cymarose

B-(40) D-Sorbose

B-(41) L-Sorbose

B-(42) D-Tagatose

B-(43) D-Fucose

B-(44) L-Fucose

B-(45) 2-Deoxy-D-glucose

B-(46) D-Psicose

B-(47) D-Fructose

B-(48) L-Fructose

B-(49) L-Rhamnose

B-(50) D-Glucosamine

B-(51) D-Galactosamine

B-(52) D-Mannosamine

B-(53) D-Glycero-D-galacto-heptose

B-(54) D-Glycero-D-manno-heptose

B-(55) D-Glycero-L-manno-heptose

B-(56) D-Glycero-D-gulo-heptose

B-(57) D-Glycero-D-ido-heptose

B-(58) D-Glycero-L-gluco-heptose

B-(59) D-Glycero-L-talo-heptose

B-(60) D-Altro-heptulose

B-(61) D-Manno-heptulose

B-(62) D-Altro-3-heptulose

B-(63) D-Glucuronic acid

B-(64) L-Glucuronic acid

B-(65) N-Acetyl-D-glucosamine

B-(66) Glycerin

B-(67) D-Threitol

B-(68) L-Threitol

B-(69) Erithritol

B-(70) D-Arabitol

B-(71) L-Arabitol

B-(72) Adonitol

B-(73) Xylitol

B-(74) D-Sorbitol

B-(75) L-Sorbitol

B-(76) D-Mannitol

B-(77) L-Mannitol

B-(78) D-Iditol

B-(79) L-Iditol

B-(80) D-Talitol

B-(81) L-Talitol

B-(82) Dulcitol

B-(83) Allodulcitol

Among these exemplified compounds, as preferable sugar alcohols, therecan be compounds B-(66) to (83), as more preferable sugar alcohols,there can be compounds B-(69) and compounds (74) to (83).

The example of the polysaccharide derivative of the invention is listedbelow, but is not limited thereto.

Exemplified Compounds

C-(1) Malt sugar

C-(2) Cellobiose

C-(3) Trehalose

C-(4) Gentiobiose

C-(5) Isomaltose

C-(6) Lactose

C-(7) Raffinose

C-(8) Gentianose

C-(9) Stachyose

C-(10) Xylan

C-(11) Araban

C-(12) Glycogen

C-(13) Dextran

C-(14) Inulin

C-(15) Levan

C-(16) Galactan

C-(17) Agarose

C-(18) Amylose

C-(19) Sucrose

C-(20) Agarobiose

C-(21) Methylcellulose

C-(22) Di-methylcellulose

C-(23) Tri-methylcellulose

C-(24) Ethylcellulose

C-(25) Di-ethylcellulose

C-(26) Tri-ethylcellulose

C-(27) Carboxymethylcellulose

C-(28) Carboxyethylcellulose

C-(29) Aminoethylcellulose

C-(30) Hydroxymethylcellulose

C-(31) Hydroxyethylcellulose

C-(32) Hydroxypropylcellulose

C-(33) Hydroxypropylmethylcellulose

C-(34) Hydroxypropylmethylcelluloseacetatesuccinate

C-(35) Carboxymethylhydroxyethylcellulose

C-(36) α-Dextrin

C-(37) β-Dextrin

C-(38) γ-Dextrin

C-(39) δ-Dextrin

C-(40) ε-Dextrin

C-(41) α-Limiting-dextrin

C-(42) β-Limiting-dextrin

C-(43) Phosphorylase-limiting-dextrin

C-(44) Soluble starch

C-(45) Thin paste starch

C-(46) White dextrin

C-(47) Yellow dextrin

C-(48) British gum

C-(49) α-Cyclodextrin

C-(50) β-Cyclodextrin

C-(51) γ-Cyclodextrin

C-(52) Metyl-α-cyclodextrin

(53) Metyl-β-cyclodextrin

C-(54) Metyl-γ-cyclodextrin

C-(55) Hydroxypropyl-α-cyclodextrin

C-(56) Hydroxypropyl-β-cyclodextrin

C-(57) Hydroxypropyl-γ-cyclodextrin

C-(58) Maltcyclodextrin

Some kinds of sugars exist naturally and widely and can be easilyobtained from the market and their derivatives can be easily synthesizedthrough reduction, oxidation or dehydration reaction.

Subsequently, the compound represented by formula (2) is explained indetail below:

    HO--(A.sub.1 --O)m.sub.1 --(A.sub.2 --O)m.sub.2 --(A.sub.3 --O)m.sub.3 --Hformula (2)

Wherein A₁, A₂ and A₃ independently represent a substituted, anunsubstituted straight or branched alkyl group and these may be the sameor different.

As the substituents, there can be a hydroxy group, a carboxy group, asulfonyl group, an alkoxy group, a carbamoyl group and a sulfamoylgroup. It is preferable that each of A₁, A₂ and A₃ has no substituentand it is the most preferable that each of A₁, A₂ and A₃ is --CH₂ CH₂ --or --CH(CH₃)--CH₂ --. m₁, m₂ and m₃ independently represent an integerof 0 to 500, provided with m₁ +m₂ +m₃ ≧5.

Among them, it is preferable that at least one of m₁, m₂ and m₃ is notless than 15, more preferable not less than 20.

In the case of that the compound represented by formula (2) is acopolymer obtained by copolymerization of monomer A and B, for example,the following dispositions are included.

-A-B-A-B-A-B-A-B-A-B-

-A-A-B-A-B-B-A-A-A-B-A-A-B-B-A-

-A-A-A-A-A-A-B-B-B-B-B -B-A-A-A-A-A-

Among these copolymers, the most preferable copolymer is ablock-copolymer (trade name; Pluronic (nonionic surfactant)) representedby the following formula (2-1), which is obtained by thecopolymerization of a etyleneglycol and a propyleneglycol.

    HO--(CH.sub.2 CH.sub.2 --O)m.sub.4 --[CH(CH.sub.3)CH.sub.2 --O]m.sub.5 --(CH.sub.2 CH.sub.2 --O)m.sub.6 --H                      Formula (2-1)

Wherein m₄, m₅ and m₆ are synonymous with m₁, m₂ and m₃ respectively.

As to the compound represented by formula (2-1) of the invention, thecontent of ethylene oxide is preferably not less than 70 weight % oftotal weight of the copolymer, especially preferably not less than 80weight % of total weight of the copolymer.

The example of the compounds represented by formula (2) and formula(2-1) of the invention is listed below, but is not limited thereto.

    ______________________________________                                                          average                                                       HO--(CH.sub.2 --CH.sub.2 --O).sub.n' --H molecular weight                   ______________________________________                                          2-1  300                                                                      2-2  600                                                                      2-3 1000                                                                      2-4 1500                                                                      2-5 2000                                                                      2-6 3000                                                                      2-7 4000                                                                      2-8 6000                                                                      2-9 10000                                                                     2-10 15000                                                                    2-11 20000                                                                    2-12 30000                                                                  ______________________________________                                        HO--(CH.sub.2 CH.sub.2 --O).sub.a' --                                                           content of                                                                              average                                             [CH(CH.sub.3)--CH.sub.2 --O].sub.b'-- ethylene molecular                      (CH.sub.2 CH.sub.2 --O).sub.c' --H oxide weight                             ______________________________________                                          2-1-1 80 weight % 8350                                                        2-1-2 80 weight % 10800                                                       2-1-3 50 weight % 4600                                                        2-1-4 70 weight % 6500                                                        2-1-5 80 weight % 5000                                                        2-1-6 50 weight % 3500                                                        2-1-7 70 weight % 7850                                                        2-1-8 50 weight % 4150                                                      ______________________________________                                    

Wherein n' is an integer not less than 5 and a', b' and c' aresynonymous with m₁, m₂ and m₃ respectively.

Among the compounds represented by formula (2) and formula (2-1) of theinvention, most preferable is polyethylene glycol (abbreviated as PEG).

As to the polyethylene glycol, an average molecular weight of 2000 to20000 is preferable, especially preferable is 3000 to 15000. The averagemolecular weight is the molecular weight obtained by calculatinghydroxyl value.

With regard to using the compound represented by formula (2), thecompound may be used singly or in combination.

The compound represented by following formula (3) is preferablycontained in the solid processing composition of the invention.

    R--(O).sub.X S.sub.Y O.sub.Z M                             Formula (3)

wherein R represents a substituted or an unsubstituted aliphatic group,an aromatic group or a heterocyclic ring group, X is 0 or 1, Y is 1 or2, Z is 2 to 8, and M represents a cation.

In formula (3) above, as an aliphatic group represented by R is cited analkyl group, an alkenyl group and an alkinyl group. As examples of alkylgroup are cited methyl, ethyl, i-propyl, butyl, t-butyl, pentyl,cyclopentyl, hexyl, cyclohexyl, octyl, dodecyl. The above alkyl groupsmay be substituted by a halogen atom (a chlorine, bromine and fluorineatom), an alkoxy group (for example, methoxy, ethoxy, 1,1-dimetylethoxy,hexyloxy and dodecyloxy), an aryloxy group (for example, phenoxy andnaphtyloxy), an aryl group (for example, phenyl and naphthyl), analkoxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl,butoxycarbonyl and 2-ethylhexylcarbonyl), an aryloxycarbonyl group (forexample, phenoxycarbonyl and naphthyloxycarbonyl), an alkenyl group (forexample, vinyl and allyl), a heterocyclic ring group (for example,2-pyridyl, 3-pyridyl, 4-pyridyl, morphoryl, piperidyl, piperazyl,pyrimidyl, pyrazolinyl and furyl), an alkinyl group (for example,propargyl), an amino group (for example, amino, N,N-dimethylamino andanilino), a cyano group, a sulfonamido group (for example,methylsulfonylamino, ethylsulfonylamino, butylsulfonylamino,octylsulfonylamino and phenylsulfonylamino).

As examples of alkenyl group are cited a vinyl group and an allyl group.As example of alkinyl group is cited a propargyl group.

As examples of aromatic groups are cited a phenyl group and a naphthylgroup. As examples of heterocyclic ring groups are cited a pyridyl group(for example, 2-pyridyl, 3-pyridyl and 4-pyridyl), a thiazolyl group, anoxazolyl group, an imidazolyl group, a furyl group, a thienyl group, apyrrolyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinylgroup, a selenazolyl, a suloforanyl group, a piperidinyl group, apyrazolyl group and a tetrazolyl group.

These alkenyl group, alkinyl group, aromatic group and heterocyclic ringgroup mentioned above can be substituted by the same substituents asused for the alkyl group represented by R as explained above in detail.

As example of cation is cited a metal ion or an organic cation. Asexamples of metal ions are cited a lithium ion, a sodium ion and apotassium ion and as examples of organic cations are cited an ammoniumion (for example, ammonium ion, tetra-methylammonium ion andtetra-butylammonium ion), a phosphonium ion (for example,tetra-phenylphosphonium ion) and a guanidyl ion.

The compound represented by formula (3) can improve a sliding propertyof the solid processing composition of the invention when thesecompounds represented by formula (3) is added when molding a tablet bycompression molding method.

The example of the compound represented by formula (3) is listed below,but is not limited thereto.

Exemplified Compounds

    C.sub.2 H.sub.5 SO.sub.3 Na                                3-1

    CH.sub.3 (CH.sub.2).sub.6 SO.sub.3 Na                      3-2

    CH.sub.3 (CH.sub.2).sub.7 SO.sub.3 Na                      3-3

    CH.sub.3 (CH.sub.2).sub.5 OSO.sub.3 Na                     3-4

    CH.sub.3 (CH.sub.2).sub.6 OSO.sub.3 Na                     3-5

    CH.sub.3 (CH.sub.2).sub.7 OSO.sub.3 Na                     3-6

    CH.sub.3 (CH.sub.2).sub.2 SO.sub.3 Na                      3-7 ##STR3##

The content of the compound represented by the above formula (3) addedinto the solid processing composition of the invention is preferably0.01 to 5.0% of the total weight of the solid processing composition,more preferably 0.1 to 2.0%, especially preferably 0.5 to 2.0%.

The application of the solid processing composition obtained by themethod of the invention to the solid developing composition is explainedin detail below.

The tablet of developing agents used in this invention includespreferably reductone derivatives such as ascorbic acid and erythorbicacid (steric isomers).

Furthermore, the following developing agents may be included. Theexamples of them are dihydroxybenzene derivatives (for example,hydroquinone, clorohydroquinone, bromohydroquinone, diclorohydroquinone,iso-propyl hydroquinone, methylhydroquinone, 2,3-diclorohydroquinone,methoxyhydroquinone, 2,5-dimethylhydroquinone, potassiumhydroquinone-monosulfonate, sodium hydroquinone-monosulfonate),3-pyrazolidone derivatives (for example, 1-phenyl-3-pyrazolidone,1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone,1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone,1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone,1-phenyl-4,4-hydroxymethyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone,1-phenyl-2-acetyl-4,4-dimethyl-3-pyrazolidone,1-(2-benzthiazole)-3-pyrazolidone, 3-acetoxy-1-phenyl-3-pyrazolidone),aminophenol derivatives (for example, o-aminophenol, p-aminophenol,N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol),1-aryl-3-aminopyrazoline derivatives (for example,1-(p-hydroxyphenyl)-3-aminopyrazoline,1-(p-methylaminophenyl)-3-aminopyrazoline,1-(p-amino-m-methylphenyl)-3-aminopyrazoline), and pyrazolonederivatives (for example, 4-amino pyrazolone), and the mixture of thesederivatives.

The developer tablet preferably contains sulfite and/or metabisulfite.The amount of sulfite when the developing tablet is dissolved in waterto provide a developing solution is 0.05 to 0.3 mol per liter,preferably 0.1 to 0.3 mol per liter.

The developer tablet may contain buffer agents (for example, carbonate,boric acid, borate and alkanol amine), alkaline agents, auxiliarysolubilizing agents (for example, polyethylene glycol derivatives andtheir ether derivatives), pH adjusting agents (for example, organicacids such as citric acid), sensitizers (for example, quaternaryammonium salts), developing accelerators, hardeners (for example,dialdehyde derivatives such as glutaraldehyde), surfactants, organicantifoggants (for example, azole compounds such as indazole compounds,imidazole compounds, benzimidazole compounds, triazole compounds,benztriazole compounds, tetrazole compounds and thiadiazole compounds),and chelating agents to form chelation with calcium ion contained incity water (for example, sodium hexametaphosphate, calciumhexametaphosphate, polyphosphate salts and diethylenetriaminepentaaceticacid). Furthermore, the developer tablet may contain anti-silver stainagents such as described in Japanese Patent Publication Open to PublicInspection (hereinafter referred to as Japanese Patent O.P.I.Publication) No.56-24347/1981.

The pH of the developing solution obtained from the developer tablet ispreferably not more than 10.5, more preferably 9.0 to 10.0.

The developing solution obtained from the developer tablet may containan amino derivative such as alkanol amine described in Japanese PatentO.P.I. Publication No.56-106244/1981.

Besides, the developing solution obtained from the developer tablet maycontain the various agents described in "Photographic ProcessingChemistry", written by L. F. A. Mason published by Focal Press Ltd. in1966, pp. 22-229, and U.S. Pat. Nos. 2,193,015 and 2,592,364, andJapanese Patent O.P.I. Publication No.48-64933/1973.

As a preferable alkaline agent is cited a carbonate which has abuffering activity. The examples of the carbonates are potassiumcarbonate, sodium carbonate and lithium carbonate and the amount of thecarbonate in developing solution is preferably 0.3 to 0.8 mol per liter.

The fix solution is explained below.

It is preferable to prepare the fix solution by adjusting and dissolvingthe solid fixing composition. As a main fixing agent, a thiosulfate saltis preferably contained. The embodiments of thiosulfate salts are saltsof a lithium thiosulfate, a potassium thiosulfate, a sodium thiosulfateand an ammonium thiosulfate, preferably used are the ammoniumthiosulfate and the sodium thiosulfate which can facilitate the fixingrate.

Besides, as main fixing agents, an iodide salt and a thiocyanide can beused. The fix solution contains a sulfite. As the sulfite, are used alithium sulfite, a potassium sulfite, a sodium sulfite and an ammoniumsulfite.

The fix solution can contain an aqueous soluble chromium salt and aaqueous soluble aluminum salt. The example of the aqueous solublechromium salt is a chromium alum and the examples of the aqueous solublealuminum salt are an aluminum sulfate and a potassium aluminum chlorideand an aluminum chloride.

The fix solution used in this invention can preferably contain compoundsconsisting of an acetic acid ion such as an acetic acid, a lithiumacetate, a potassium acetate, a sodium acetate and an ammonium acetate.The sodium acetate and ammonium acetate are more preferably used.

Furthermore, the fix solution can contain a citric acid, a tartaricacid, a malic acid, a succinic acid and a phenylacetic acid and theiroptical isomers.

The salts of these acids are preferably the salts obtained with lithium,potassium, sodium and ammonium. The examples of these salts are apotassium citrate, a sodium citrate, an ammonium citrate, a lithiumhydrogentartrate, a potassium hydrogentartrate, a potassium tartrate, ssodium hydrogentartrate, a sodium tartrate, an ammoniumhydrogentartrate, a potassium ammonium tartrate, a potassium sodiumtartrate, a sodium malate, an ammonium malate, a sodium succinate and anammonium succinate.

Among the compounds mentioned above, more preferable are citric acid,iso-citric acid, malic acid and phenyl acetic acid and their salts. Asthe other acids are cited not only inorganic acids such as sulfuricacid, hydrochloric acid, nitric acid and boric acid, but also organicacids such as formic acid, propionic acid, oxalic acid and malic acid,preferable are boric acid and aminipolycarboxylic acid and their salts.

As for chelating agents, are cited aminopolycarboxylic acids such asnitrilotriacetic acid and ethylenediaminetetraacetic acid.

As for surfactants, are cited anion surfactants such as sulfuricesterified compound and sulfonated compound, non- ionic surfactants suchas polyethyleneglycol and esterified compound, and amphotericsurfactants. As for wetting agents, are cited alkanol amine andalkyleneglycol.

As for fix accelerating agents, are cited thiourea derivatives andalcohol derivatives having triple bond in their molecules and thioetherderivatives.

The pH of fix solution is not less than 3.8, preferably 4.2 to 5.5.

The amount of replenisher of both developing solution and fixingsolution related to this invention is preferably not more than 20 ml per10×12 inch² size from the viewpoint of the reduction of the wastesolution, more preferably not more than 15 ml per 10×12 inch² size.

EXAMPLES

The examples of the invention will be explained below, but the inventionis not limited thereto.

Example 1 Preparation of the Solid Processing Composition for DevelopingSolution

As the stirring granulation machine, Henschel mixer FM20C/I typeproduced by Mitsui Mining Co., Ltd. whose maximum capacity was 20 liter,was used. Two stirring blades were equipped.

As the lower blade near the bottom mixing vessel, Ao type (for generaluse) was equipped, and as the upper blade, Zo type (for kneading use)was equipped. The temperature in the mixing vessel was adjusted bycirculating warm water set up as described in Table 1 and 2 through thejacket surrounding the mixing vessel of Henschel mixer.

The temperature adjusted in the granulation process was shown in Table 1and 2.

    ______________________________________                                        [Preparation of solid developer composition]                                  ______________________________________                                        (1) Compound represented by formula (1)                                                             1700 g                                                     (see Table 1, 2)                                                             (2) Sodium metabisulfite 500 g                                                (3) 1-Phenyl-3-pyrazolidone 150 g                                             (4) N-Acetyl-D,L-penicillamine  5 g                                           (5) Glutaraldehyde-bisodiumsulfite 200 g                                      (6) Sugar derivative 250 g                                                     (see Table 1, 2)                                                             (7) Compound represented by formula (3)  28 g                                  (see Table 1, 2)                                                           ______________________________________                                    

Granulation

The granulation was performed by changing the combination ofabove-mentioned processing agents (1) to (7) as shown in Table 1 and 2.First, the processing agents (1) to (6) were added into the mixingvessel as shown in Table 1 and 2. Hereinafter, the granulation processof the invention was divided as follows for convenience.

Process A: stirring mixture.

Process B: granulation process by pouring water.

Process C: stirring mixture to facilitate granulation still more.

By dividing the granulation process into these three processes, thepowdery granule was produced under the condition shown in Table 1 and 2.In the case of temperature difference between the above-mentionedprocesses, next process is performed after adjusting the temperature ofthe jacket water. Furthermore, the compound (7), which is represented byformula (3), was added into the mixing vessel after finishing theprocess C, and was stirred still more 30 seconds.

The rotation rate of the stirring blades was 600 rpm in the process A,1800 rpm in the process B, and 600 rpm in the process C.

Water was dropped into the mixing vessel constantly by using a pipettefor time set up in the process B shown in Table 1 and 2.

Measurement of Particle Diameter of the Powdery Granule

The particle distribution was measured by using both microelectromagnetic vibration sieve M-100 produced by Tsutsui RikagakukikaiCo., Ltd. and sieve analysis with mesh standardized by JapaneseIndustrial Standard (JIS). The vibration time was 5 minutes.

Producing Tablet

The obtained powdery granules were tableted in an amount per tablet of10 g, using the tableting machine which was improved type of the rotarytableting machine such as Tough Press Correct Model 1527HU produced byKikusui Seisakusho Co., Ltd. The cylindrical developer tablet with thediameter of 30 mm was obtained.

Evaluation of Tablet Hardness

Each of several groups consisting of twenty fresh developer tabletscontaining the same ingredients was prepared. The hardness of thesefresh developer tablets obtained by the above method was measured byusing a hardness measuring machine (TS-75NL produced by Okada SeikoshaCo., Ltd.), and an average value of the hardness of each of severalgroups consisting of twenty tablets was defined as the hardness oftablet in this invention. The larger hardness of tablet expresses anexcellent tablet and more than 35 kg of hardness is a preferablehardness for practical use.

Evaluation of Tablet Storage Hardness

Each of several groups consisting of twenty tablets was enclosed in amoistureproof bag made from polyethylene terephthalate which wasvacuum-evaporated by aluminum. Each bag was allowed to stand under thehigh constant temperature 50° C. for 30 days, and to check up the heatresistance of the tablet, the hardness of these tablets preserved underthe high constant temperature was evaluated in the similar manner asused in evaluating the hardness of fresh tablets mentioned above.

The results thereof will be shown collectively in Table 1 and 2.

                                      TABLE 1                                     __________________________________________________________________________                                                  Parti-   Tablet                      Process    cle dia-  hard-                                                 Formula  Formula B    meter not Tablet ness                                   (1)  (3) amount of Process A Process B Process C more than hard- after         Com-     Com- water                                                                              Temp.                                                                             Time                                                                              Temp.                                                                             Time                                                                              Temp.                                                                             Time                                                                              150 μm                                                                          ness                                                                              storage                                                                           Re-                  No. pound Sugar pound (wt %) (° C.) (min.) (° C.) (min.)                                                                 (° C.)                                                                 (min.) (wt %)                                                                 (kg) (kg)          __________________________________________________________________________                                                               marks              1  Sodium                                                                             D-  Sodium 1-                                                                          0.5  25  1.0 25  5.0 25  10.0                                                                              89   12  5   Comp.                 erythor- Sorbi- hexane-                                                       bate tol sulfonate                                                           2 Sodium D- Sodium 1- 0.5 50 1.0 25 5.0 25 10.0 83 35 39 Inv.                  erythor- Sorbi- hexane-                                                       bate tol sulfonate                                                           3 Sodium D- Sodium 1- 0.5 25 1.0 50 5.0 25 10.0 75 43 45 Inv.                  erythor- Sorbi- hexane-                                                       bate tol sulfonate                                                           4 Sodium D- Sodium 1- 0.5 25 1.0 25 5.0 50 10.0 80 50 85 Inv.                  erythor- Sorbi- hexane-                                                       bate tol sulfonate                                                           5 Sodium D- Sodium 1- 0.5 25 3.0 25 5.0 25 10.0 81 12 5 Comp.                  erythor- Sorbi- hexane-                                                       bate tol sulfonate                                                           6 Sodium D- Sodium 1- 0.5 50 3.0 25 5.0 25 30.0 80 35 45 Inv.                  erythor- Sorbi- hexane-                                                       bate tol sulfonate                                                           7 Sodium D- Sodium 1- 0.5 25 3.0 50 5.0 25 30.0 64 42 45 Inv.                  erythor- Sorbi- hexane-                                                       bate tol sulfonate                                                           8 Sodium D- Sodium 1- 0.5 25 3.0 25 5.0 50 30.0 70 55 94 Inv.                  erythor- Sorbi- hexane-                                                       bate tol sulfonate                                                           9 Sodium D- Sodium 1- 0.5 60 1.0 25 5.0 25 30.0 77 36 48 Inv.                  erythor- Sorbi- hexane-                                                       bate tol sulfonate                                                           10 Sodium D- Sodium 1- 0.5 25 1.0 60 5.0 25 30.0 66 45 50 Inv.                 erythor- Sorbi- hexane-                                                       bate tol sulfonate                                                           11 Sodium D- Sodium 1- 0.5 25 1.0 25 5.0 60 30.0 80 59 95 Inv.                 erythor- Sorbi- hexane-                                                       bate tol sulfonate                                                           12 Sodium D- Sodium 1- 0.5 25 1.0 25 5.0 70 30.0 73 60 100 Inv.                                                                          erythor-                                                                    Sorbi- hexane-        bate tol sulfonate                                                           13 Sodium D- Sodium 1- 0.5 25 1.0 25 5.0 85 30.0 70 62 104 Inv.                                                                          erythor-                                                                    Sorbi- hexane-        bate tol sulfonate                                                           14 Sodium D-man- Sodium 1- 0.5 25 1.0 25 5.0 25 30.0 90 13 5 Comp.                                                                       erythor-                                                                    nitol hexane-                                                                   bate                                                                        sulfonate          __________________________________________________________________________     Comp.: Comparison, Inv.: Invention                                       

                                      TABLE 2                                     __________________________________________________________________________                                                  Parti-   Tablet                      Process    cle dia-  hard-                                                 Formula  Formula B    meter not Tablet ness                                   (1)  (3) amount of Process A Process B Process C more than hard- after         Com-     Com- water                                                                              Temp.                                                                             Time                                                                              Temp.                                                                             Time                                                                              Temp.                                                                             Time                                                                              150 μm                                                                          ness                                                                              storage                                                                           Re-                  No. pound Sugar pound (wt %) (° C.) (min.) (° C.) (min.)                                                                 (° C.)                                                                 (min.) (wt %)                                                                 (kg) (kg)          __________________________________________________________________________                                                               marks              15 Sodium                                                                             D-man-                                                                            Sodium 1-                                                                          0.5  25  1.0 25  5.0 33  30.0                                                                              87   15  10  Comp.                 erythor- nitol hexane-                                                        bate  sulfonate                                                              16 Sodium D-man- Sodium 1- 0.5 25 1.0 25 5.0 33 60.0 84 18 11 Comp.                                                                      erythor-                                                                    nitol hexane-                                                                   bate                                                                        sulfonate                                                                      17 Sodium                                                                    D-man- Sodium                                                                 1- 0.5 25 1.0                                                                 25 5.0 39 60.0                                                                72 40 56 Inv.                                                                   erythor-                                                                    nitol hexane-                                                                   bate                                                                        sulfonate                                                                      18 Sodium                                                                    D-man- Sodium                                                                 1- 1.8 25 1.0                                                                 25 5.0 39 60.0                                                                67 45 63 Inv.                                                                   erythor-                                                                    nitol hexane-                                                                   bate                                                                        sulfonate                                                                      19 Sodium                                                                    D-man- Sodium                                                                 1- 0.5 25 1.0                                                                 25 5.0 50 30.0                                                                72 50 83 Inv.                                                                   erythor-                                                                    nitol hexane-                                                                   bate                                                                        sulfonate                                                                      20 Sodium                                                                    D-man- Sodium                                                                 1- 0.5 25 1.0                                                                 25 5.0 60 30.0                                                                75 55 88 Inv.                                                                   erythor-                                                                    nitol hexane-                                                                   bate                                                                        sulfonate                                                                      21 Sodium                                                                    D-man- Sodium                                                                 1- 0.5 25 1.0                                                                 25 5.0 70 30.0                                                                75 59 90 Inv.                                                                   erythor-                                                                    nitol hexane-                                                                   bate                                                                        sulfonate                                                                      22 Sodium                                                                    D-man- Sodium                                                                 1- 0.5 25 1.0                                                                 25 5.0 85 30.0                                                                77 64 97 Inv.                                                                   erythor-                                                                    nitol hexane-                                                                   bate                                                                        sulfonate                                                                      23 Sodium                                                                    D-man- Sodium                                                                 1- 0.1 25 1.0                                                                 25 5.0 60 30.0                                                                87 46 53 Inv.                                                                   erythor-                                                                    nitol hexane-                                                                   bate                                                                        sulfonate                                                                      24 Sodium                                                                    D-man- Sodium                                                                 1- 1.0 25 1.0                                                                 25 5.0 60 30.0                                                                75 52 85 Inv.                                                                   erythor-                                                                    nitol hexane-                                                                   bate                                                                        sulfonate                                                                      25 Sodium                                                                    D-man- Sodium                                                                 1- 1.8 25 1.0                                                                 25 5.0 60 30.0                                                                64 70 47 Inv.                                                                   erythor-                                                                    nitol hexane-                                                                   bate                                                                        sulfonate                                                                      26 Sodium                                                                    D-man- Sodium                                                                 1- 3.0 25 1.0                                                                 25 5.0 60 30.0                                                                48 82 32 Inv.                                                                   erythor-                                                                    nitol hexane-                                                                   bate                                                                        sulfonate                                                                      27 Sodium D-                                                                 Sodium 1- 0.5                                                                 25 1.0 25 5.0                                                                 60 30.0 77 59                                                                 103 Inv.                                                                        erythor-                                                                    Sorbi- octane-        bate tol sulfonate                                                           28 Sodium D- Sodium 1- 1.8 25 1.0 25 5.0 60 30.0 65 65 115 Inv.                                                                          erythor-                                                                    Sorbi- octane-        bate tol sulfonate                                                         __________________________________________________________________________     Comp.: Comparison, Inv.: Invention                                       

As is obvious from the results shown in Table 1 and 2, it can be foundthat every solid processing composition sample of the invention has anexcellent tablet hardness.

Example 2

Polyethylene glycol (PEG) represented by formula (2) was added into thesolid developer composition of example 1 and the tablet of the soliddeveloper composition was prepared in the similar manner as described inexample 1. The resulted tablet samples were evaluated in the similarmanner as described in example 1. The solubility of the tablet wasevaluated by following method.

Evaluation of Tablet Solubility

Each of several groups consisting of six tablets containing the sameingredients was prepared and dissolved in a liter of warm water of 30°C. maintained constantly using magnetic stirrer. The time between addingeach group of six tablets into a liter of warm water of 30° C. andcomplete dissolution of all the six tablets checked up by a visualobservation was measured.

The results thereof will be shown in Table 3.

                                      TABLE 3                                     __________________________________________________________________________    Compound (PEG)                                                                  of Formula (2) Process                                                      Average         B                                                               molec- Added  amount of Process A Process B Process C                          ular posi-                                                                             Added                                                                             water                                                                              Temp.                                                                             Time                                                                              Temp.                                                                             Time                                                                              Temp.                                                                             Time                                   No. weight tion amount (wt %) (° C.) (min.) (° C.) (min.)                                              (° C.) (min.)                 __________________________________________________________________________    29 --  --   --  0.4  55  1   25  30  25  30                                     30 4000 Process A 75 0.4 55 1 25 30 25 30                                     31 4000 Process B 75 0.4 55 1 25 30 25 30                                     32 4000 Process C 75 0.4 55 1 25 30 25 30                                     33 -- -- -- 0.4 25 1 55 30 25 30                                              34 4000 Process A 75 0.4 25 1 55 30 25 30                                     35 4000 Process B 75 0.4 25 1 55 30 25 30                                     36 4000 Process C 75 0.4 25 1 55 30 25 30                                     37 -- -- -- 0.4 25 1 25 30 55 30                                              38 4000 Process A 75 0.4 25 1 25 30 55 30                                     39 4000 Process B 75 0.4 25 1 25 30 55 30                                     40 4000 Process C 75 0.4 25 1 25 30 55 30                                     41 4000 Process C 75 0.1 25 1 25 30 55 30                                     42 4000 Process C 75 1.0 25 1 25 30 55 30                                     43 4000 Process C 75 1.8 25 1 25 30 55 30                                     44 4000 Process C 75 3.0 25 1 25 30 55 30                                     45 6000 Process C 75 0.5 25 1 25 30 55 30                                     46 6000 Process C 75 1.0 25 1 25 30 55 30                                     47 6000 Process C 75 1.8 25 1 25 30 55 30                                     48 6000 Process C 75 3.0 25 1 25 30 55 30                                   __________________________________________________________________________       Particle diameter                                                             not more Tablet hardness Tablet hardness after                               No. than 150 mm (wt %) (kg) storage (kg) Tablet Solubility (min.)                                                   Remarks                               __________________________________________________________________________      29 78 35 45 24.0 Invention                                                    30 62 64 105 17.9 Invention                                                   31 70 55 93 17.7 Invention                                                    32 70 57 97 17.0 Invention                                                    33 73 48 53 28.0 Invention                                                    34 65 70 120 16.5 Invention                                                   35 65 82 128 16.0 Invention                                                   36 62 88 135 16.0 Invention                                                   37 78 55 90 31.0 Invention                                                    38 72 72 118 14.0 Invention                                                   39 64 85 130 13.5 Invention                                                   40 62 89 140 13.2 Invention                                                   41 82 95 105 19.0 Invention                                                   42 71 92 100 13.0 Invention                                                   43 64 100 65 13.0 Invention                                                   44 41 108 34 14.5 Invention                                                   45 65 80 125 17.8 Invention                                                   46 69 85 92 17.5 Invention                                                    47 65 93 60 17.0 Invention                                                    48 38 105 33 16.0 Invention                                                 __________________________________________________________________________

As is obvious from the results shown in Table 3, it can be found thatthe solid processing composition of the invention which is fresh orpreserved under the high constant temperature of 50° C. for 30 days hasan excellent tablet hardness, and it is also obvious that by addingpolyethylene glycol derivatives into the solid processing composition ofthe invention, the solubility of the tablets is extremely increased andhandling the tablets is improved when they are dissolved.

The following developing additives were added into the prescription ofthe solid developer composition used in Example 1, and then a developingsolution of 50 liter was made by adding water.

    ______________________________________                                        (1) Potassium carbonate  4300 g                                                 (2) Sodium diethylenetriaminepentaacetate 85 g                                (3) 3-(5-Mercaptotetrazole-1-yl)benzenesulfonic acid 20 g                     (4) Potassium iodide  3 g                                                   ______________________________________                                    

The obtained developer was placed in the developing tank of a rollercarrying automatic developing machine, SRX-201 (produced by KonicaCorporation), and the rest of the developer was placed in an auxiliarytank. On the other hand, the fixing solution, TC-F1 (produced by KonicaCorporation), was used. X-ray film SRG which was exposed to X-raythrough the breast phantom was processed by this developing solution andthis fixing solution. The total processing time was 60 seconds in termsof Dry to Dry. The results obtained by the above processing solutionsshowed similar photographic characteristics compared with the resultsobtained with current processing solutions.

The manufacturing cost of the solid processing composition of theinvention can be reduced by 30% compared with the manufacturing cost ofthe current solid processing composition, because the manufacture of thesolid processing composition of the invention does not include dryingand dressing process.

What is claimed is:
 1. A method for manufacturing a solid processingcomposition for processing a silver halide photographic light sensitivephotographic material, wherein the composition is manufactured by astirring granulation method comprising a stirring granulation process,and at least part of said stirring granulation process is performedunder the temperature condition of 35° C. to 120° C.
 2. The method formanufacturing the solid processing composition of claim 1, wherein thecontent of the added solution in the stirring granulation process is0.01 to 2.0 weight % of the total weight of said solid processingcomposition.
 3. The method for manufacturing the solid processingcomposition of claim 1, wherein not less than 60% of the total weight ofsaid solid processing composition has particle diameter of 1.0 μm to 150μm.
 4. The method for manufacturing the solid processing composition ofclaim 1, wherein the composition contains reductone derivativerepresented by the following formula (1): ##STR4## wherein R₁ and R₂independently represent a hydroxy group, an amino group, an acylaminogroup, an alkylsulfonylamino group, an arylsulfonylamino group, analkoxycarbonylamino group, a mercapto group or an alkylthio group; and Xrepresents an atomic group necessary to form a 5- or 6-membered ring. 5.The method for manufacturing the solid processing composition of claim1, wherein the composition contains at least one kind of sugar and thecompound represented by the following formula (2):

    HO--(A.sub.1 --O)m.sub.1 --(A.sub.2 --O)m.sub.2 --(A.sub.3 --O)m.sub.3 --Hformula (2)

wherein A₁, A₂ and A₃ independently represent a substituted or anunsubstituted straight or branched alkyl group and these may be the sameor different, m₁, m₂ and m₃ independently represent an integer of 0 to500, provided with m₁ +m₂ +m₃ ≧5.
 6. The method for manufacturing thesolid processing composition described in claim 3 wherein the solidprocessing composition is molded as a tablet form by compression moldingmethod.
 7. The method for manufacturing the solid processing compositionof claim 1 wherein said stirring granulation process comprises the stepsof stirring ingredients for the solid processing composition,granulating the ingredients by pouring a solution and stirringgranulated mixture.
 8. The method for manufacturing the solid processingcomposition of claim 7 wherein the time performed under the temperatureis 30 seconds to 180 minutes.
 9. The method for manufacturing the solidprocessing composition of claim 7 wherein the time for stirring theingredients is 3 seconds to 120 minutes.
 10. The method formanufacturing the solid processing composition of claim 7 wherein thetime for pouring the solution is 1 second to 30 minutes duringcontinuing to stir.
 11. The method for manufacturing the solidprocessing composition of claim 7 wherein the time for stirring afterpouring the solution is 30 seconds to 90 minutes.
 12. The method formanufacturing the solid processing composition of claim 1 wherein saidcomposition contains a compound represented by formula (3):

    R(O)xSyOzM                                                 formula (3)

wherein R represents an aliphatic group, an aromatic group or aheterocyclic ring group, x is 0, y is 1 or 2, z is 2 to 8, and Mrepresent a cation.
 13. The method for manufacturing the solidprocessing composition of claim 5 wherein the amount of at least onekind of said sugar and said compound represented by formula (2) is 0.5to 30 weight % of the total weight of the solid composition.
 14. Themethod of claim 1, wherein said solid processing composition is forfixing solution, the composition comprises a thiosulfate salt.
 15. Amethod for manufacturing the solid processing composition for processinga silver halide photographic light sensitive material comprising a stepsof stirring ingredients for the solid processing composition for 3seconds to 120 minutes, granulating the ingredients by pouring asolution, wherein the time of pouring the solution is 1 second to 30minutes continuing to stir and stirring granulated mixture for 30seconds to 90 minutes, wherein at least part of the steps is performedunder temperature of 35 to 120° C.
 16. The method for manufacturing thesolid processing composition of claim 15 wherein the amount of thesolution poured is 0.01 to 2.0 weight % of the total weight of saidsolid processing composition.
 17. The method of claim 16, wherein saidsolid processing composition is for developing the silver halidephotographic light sensitive material, the composition comprisesreductone derivative in an amount of 0.01 to 2.0 weight % of the totalweight of said solid processing composition.